Vat dyestuffs of the anthraquinone acridone series



Patented Jan. I932 UNITED STATES PATENT OFFICE ,FBI ITZ'BAUM AN N, OF IiEVER-KUSEN-ON-THE-RHINE, GERMANY, ASSIGNOR T0 GENERAL ANILINE WORKS, INC., OF NEW YORK,

N. Y., A CORPORATION OF DELAWARE var nYEsrUrrs or THEVANTHRAQUINONE ACRIDONE snares No Drawing. Application filed April 4,1980, Serial No. 441,794, and in Germany April 9, 1929. V

The present invention relates to new dyestuffs of the probable formula:

wherein A means a-nthraquinone to which the -NH and CO groups are attached by adjacent carbon atoms, 11 one of the numbers 7 1 or 2 and wherein the NH- group is atitached to an alpha-position of the 'dianthraquinon l amine-carbazole ring system andthe O group to theadjacent beta-position.

In accordance with the invention dyestufls of t e above mentioned formula are obtainable y reacting upon an alpha-aminoor alpha-alpha-diamino-1.1 di anthraquinonylamine-carbazole with an ortho-halogen-anthraquinone-carboxylic acid, such as 1'-chlo- 7 36' roanthraquinone-2 carboxylic acid, 2-bromoanthraquinone-l-carboxylic acid, 2-chloroanthraquinone-3-carboxylic'acid and the like, or more advantageously with an ester of such carboxylic acid, such as methyl ester, ethyl "ester, etc. We prefer to performthe reac-v tion by heating the reaction components in a suitable high boiling or anic solvent, such astrichloro benzene, nitro enzene, naphthalene, or the like inthe presence of an acid binding medium with or Without the addition of small amounts of copper or a copper salt. After reaction is complete the reaction product (a trior tetra-anthraquinonylaminecarbazole- .carboxylic acid'oran ester thereof) is isolated" in the usual manner and heated with conc.

sulfuric acid advantageously to about 90-' 100 C. whereby acridone ring closure occurs.

The products thus obtainable which probably correspond to the general formula as given in the statement of invention form reddish-brown to black powders, difliculty soluble or almost insoluble in the usual organic solvents, soluble in strong sulfuric acid with red to bluish-green colorations, dyeing cotton from an alkaline hydrosulfite vat red to olivegreen shades of excellent fast-ness to light, beingat the same time Weatherproof and ossessing a good evening color. They are urthermore valuable dyestuffs for printing textile fibers. I

The following examples illustrate my invention without restricting it thereto, the" parts being by Weight.

Ewamplel 4,4 parts of 4-amino-1.1-dianthraquinonylamine carbazole (obtainable by saponification of 4-benzoylamino-1.1-dianthraquino-' nylamine carba'zole) 3,6 parts of 2-bromo-anthraquinone-l-carboxylic acid methyl ester, 3 parts ofwater free potassium acetate, 1,4 parts of'magnesium oxide and 0,2 part of copper acetate are introduced into parts of naphthalene and the mixture is heated to about 215 C. until no more unchanged 4- amino-1.1-dianthraquinonylamine-carbazole is present. Hereafter about 200 parts of toluene are added, the reaction product is sucked off at about (1, washed with toluene and ethyl alcohol and boiled up with diluted hydrochloric acid. After drying dark olive crystals dissolving in nitro benzene with a dull green coloration are obtained, yielding a yellowish-brown hydrosulfite vat. p

WVhen dissolving this intermediate product in sulfuric acid of 96% strength an olive colored solution is first obtained, which changes to bluish-red after heating to about 100 C. whereby acridone ring closure occurs.

When pouring the solution onto ice an olive green compound separates whichis sucked off, washed with water until neutral and dried. The product thus obtainable probably corresponds to the formula I 0 It dyes cotton from a dull red alkaline hydrosulfite vat strong olive-green shadesof excellent. fastness properties and is almost 'in-- soluble in the usual organic solvents.

Y I Example 2 V 4,6 parts of 4,4 -diamino-l.1' dianthra-- quinonylamine-carbazole (obtainable by saponification of 44 (11- (benzoylamino)- 1.1 -'dianthraquinonylamine carbazole) I 8 parts of Q-bromoanthraquinone-l-carboxylic acid methyl ester, 5 parts of Water free potashsium acetate, 3 parts of magnesiumoxideand" 0,3.part ofcopper dust are boiled in1 parts o fnaphtha'lene until no more unchanged 4.4 1 diamino 1.1-dianthraquinonylamines carbazole is present.

After cooling toluene is V added, the reaction product filtered, washed,

sow,

first with-toluene then with alcohol and dried. a

A black crystallized intermediate product is thus obtained, soluble in boiling nitro benzene with an olive coloration. 7

When dissolving the product in sulfuric: acid I of 96% strength an 7 olive colored :solu- 7 tion isobtained, the color of which changes to,

bluish-green when heating whereby acridone" ring closure occurs. After working up in the;

usual manner the reaction vproduct which probably corresponds to the formula:

4,2 parts of 5.5-diamino- 1,l'-dianthraquinonylamine carbazole (obtainable by 'saponifioation of the corresponding dibenzoyl compound), 6,7 J parts 7 of i l-chloroanthraquinone 24carboxylic acid methyl ester, 5

parts ofwater free sodium acetate, 2 parts of magnesium oxide and 0,3partof copper acetate are boiled for 3-4 hours with 100 parts of naphthalene. After dilution With pyridine reddishbrown crystals separate, dissolving in 'trichlorobenzene with a reddish-brown coloration. Acridone ring closure can be performed as described in Example 1 or 2. A product is thus obtained, which probably corresponds to the formulaf Q It dissolves in strong sulfuric acid with a reddish-brown coloration, is ,difficultly solu-- ble in the'usual organic solvents and'dyes cotton from a greyish-violet hydrosulfite vat blackish-brown'shades-of good fastness properties." a

V g Y Example; 3 partsof 5.5 -diamino-l.1--dianthraquinonyl-amine-carbazole, 4.2 parts of 2-ch1o-. roanthraquinone 3 :carboxylic acid I methyl ester, 4t.parts,of water freepotassium acetateand 0,2 part of copper dust are boiled with 8Qfparts ofnaphthalenefo'r, hours.v The reaction product is isolated as described in the foregoing examples and closure of the acridone ring is performed by heating with v conc. sulfuric acid to about 100 C. After working up in the usual manner and drying a dark brown powder is obtained, which dissolves in strong sulfuric acid with a brown coloration and dyes cotton from a brown hydrosulfite Vat reddish-brown shades. The product probably corresponds to the formula NH r Q i? W a I cl aim 1. The products of the probable general formula:

wherein A means anthraquinone to which the NH and CO groups are attached by adjacent carbon atoms, 11 one of the numbers 1 or 2 and wherein the NH group is attached to an alpha-position of the dianthraquino-nyl-amine-carbazole' ring system and the CO group to the adjacent beta position, said products being reddish-brown to black powders difiicultl soluble in the'usual organic solvents, solub e in strong sulfuric acid with red to bluish-green colorations,

dyeing cotton from an alkaline hydrosulfite vat red to olive-green shades of good fastness properties.

2. The product of the probable formula: 7

o 1% said product forming olive-green flakes, dyeing cotton from a dull red alkaline hydrosulfite Vat strong olive-green shades of excellent fastness properties.

In testimony whereof, I afiix In signature.

FRITZ BA MANN. 

